WO2006060917A1 - Method for improving bitumen recovery from oil sands by production of surfactants from bitumen asphaltenes - Google Patents
Method for improving bitumen recovery from oil sands by production of surfactants from bitumen asphaltenes Download PDFInfo
- Publication number
- WO2006060917A1 WO2006060917A1 PCT/CA2005/001875 CA2005001875W WO2006060917A1 WO 2006060917 A1 WO2006060917 A1 WO 2006060917A1 CA 2005001875 W CA2005001875 W CA 2005001875W WO 2006060917 A1 WO2006060917 A1 WO 2006060917A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- bitumen
- agents
- asphaltenes
- slurry
- surfactants
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/04—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by extraction
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH DRILLING; MINING
- E21B—EARTH DRILLING, e.g. DEEP DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
- E21B43/16—Enhanced recovery methods for obtaining hydrocarbons
- E21B43/24—Enhanced recovery methods for obtaining hydrocarbons using heat, e.g. steam injection
- E21B43/243—Combustion in situ
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/205—Metal content
- C10G2300/206—Asphaltenes
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/80—Additives
Definitions
- the present invention relates to methods for increasing the efficiency of bitumen recovery from oil sands using water-slurry-based and in situ extraction processes. More particularly, the invention relates to methods for producing surfactants from bitumen asphaltenes present in oil sands, to promote the formation of bitumen-water emulsions and thereby to facilitate bitumen recovery. The invention also relates to production of stable bitumen-water emulsions as a result of the production of surfactant species from bitumen asphaltenes, to facilitate pipeline transportation of bitumen in the form of bitumen-water emulsions.
- bitumen constituting the largest oil sands deposit in the world. Since the 1960s, bitumen recovered these deposits has been upgraded to make synthetic crude oil at production rates as high as one million barrels per day.
- Bitumen is commonly recovered from the surface-mined oil sands ore using water- slurry-based extraction processes.
- Recovery of bitumen from deep oil sands formations may be accomplished by thermal methods such as underground bitumen combustion (i.e., in situ combustion, or ISC), or steam injection methods such as steam- assisted gravity drainage (SAGD) and cyclic steam simulation (CSS).
- ISC underground bitumen combustion
- SAGD steam- assisted gravity drainage
- CSS cyclic steam simulation
- Water-soluble asphaltic acids also help the formation of the bitumen- water emulsions under in situ recovery conditions, since they act as surfactants reducing surface and interfacial tensions, thereby helping to break down the oil sands ore structure and promoting the release of bitumen from the ore.
- bitumen particles or droplets If an emulsion is not sufficiently stable, the emulsified material (such as bitumen particles or droplets) will tend to flocculate or coalesce, leading to breakdown of the emulsion, which could hamper or preclude pipeline transportation of the emulsion.
- the production of surfactant species from bitumen asphaltenes would promote the formation of stable bitumen-water emulsions, thereby facilitating pipeline transportation of bitumen in the form of a bitumen- water emulsion.
- the present invention is a method for increasing the efficiency of bitumen recovery from oil sands by treating oil sands ore with chemical agents to produce surfactants from bitumen asphaltenes present in the ore.
- bitumen asphaltenes are chemically modified to form surfactant species by means of oxidation, sulfonation, sulfoxidation, or sulfomethylation reactions, or by a combination of such reactions.
- the resultant surfactants reduce surface and interfacial tensions so as to promote the release of bitumen from the ore, thus facilitating the extraction and recovery of bitumen for use in producing synthetic crude oil, and to promote the formation stable bitumen-water emulsions to facilitate transportation of bitumen by pipeline.
- Oil sands ore may be treated in accordance with the invention either in situ or after incorporation into an oil sands ore-water slurry, depending on the nature of the particular bitumen-recovery process being used.
- the methods of the invention can also be used in association with other oil sands extraction and processing steps and equipment, including but not limited to ore conditioning vessels, ore-water slurry pipeline systems, primary and secondary extraction vessels, flotation vessels, and tailings streams containing residual bitumen (including oil sands tailings, cyclone overflow streams, cyclone underflow streams, mature fine tailings, and any composite non-segregating tailings streams).
- one or more oxidation agents are introduced into an oil sands ore-water slurry or, alternatively, into a subsurface oil sands seam in conjunction with the injection of steam into the seam.
- the oxidation agent or agents may be selected from the group consisting of air oxygen (i.e., O 2 as a constituent of air), ozone (Oj), and a mixture of air oxygen and ozone.
- air oxygen i.e., O 2 as a constituent of air
- Oj ozone
- sulfonation agents are introduced into an oil sands ore-water slurry or a subsurface oil sands seam.
- the sulfonation agent may be selected from the group consisting of sulfur dioxide (SO 2 ) gas, sodium sulfite (Na 2 SOs), and sodium bi-sulfite (NaHSO 3 ).
- SO 2 sulfur dioxide
- Na 2 SOs sodium sulfite
- NaHSO 3 sodium bi-sulfite
- other chemical agents having effective sulfonation properties may also be used, without departing from the scope of the present invention.
- both oxidation agents and sulfonation agents are introduced into the slurry or subsurface seam.
- Such use of sulfonation agents in conjunction with oxidation agents may be referred to as sulfoxidation.
- sulfoxidation reactions may also be initiated by use of sulfoxidation agents such as petroleum coke utilization flue gas or other agents providing a source of both sulfur (in the form of sulfur dioxide or other compounds) and oxygen.
- the agents (or additives) referred to above will typically react only with the bitumen asphaltenes, whether in association with water-slurry-based extraction methods or in situ thermal recovery methods.
- a selected sulfonation additive could be used as the sole additive to produce surfactants from bitumen asphaltenes.
- a combination of additives could be used in simultaneous or alternating fashion.
- an ozone- air mixture would be a suitable oxidant to produce effective amounts of surfactant species by oxidizing bitumen asphaltenes in water-slurry-based extraction processes.
- an ozone- air mixture is used as an oxidation agent, and if there is a need to increase the solubility of already oxidized bitumen asphaltenes, this may be accomplished by sulfonation and sulfoxidation of asphaltenes - such as, for example, by using SO 2 .
- SO 2 sulfonation and sulfoxidation of asphaltenes -
- the injection of SO 2 is preferably made after the injection of ozone.
- Sulfoxidation of bitumen asphaltenes to improve bitumen recovery efficiency may also be accomplished by controlled injection of petroleum coke utilization flue gas into the ore-water slurry or subsurface oil sands seam.
- Petroleum coke is a by-product of known bitumen upgrading processes used in the production of synthetic crude oil from oil sands bitumen.
- Several million tons of petroleum coke are produced each year in the northern Alberta oil sands region, and tens of millions of tons are currently stockpiled.
- Petroleum coke produced from northern Alberta oil sands typically consists of about 79.9% carbon (C), 1.9% hydrogen (H), 4.6% oxygen (O 2 ), 1.7% nitrogen (N 2 ), 6.8% sulfur (S), and 7.1% ash, and has a calorific value of about 29.5 MJ/kg (megaJoules per kilogram).
- the ash is typically composed of about 41.3% silicon dioxide (SiO 2 ), 25.1% aluminum oxide (Al 2 O 3 ), 10.9% ferric oxide (Fe 2 O 3 ), 3.6% titanium dioxide (TiO 2 ), 1.3% nickel oxide (NiO), 3.7% vanadium pentoxide (V 2 O 5 ), and 14.1% other oxides, which need to be considered during the selection of the petroleum utilization process.
- Petroleum coke can be combusted directly, which may require a specially designed boiler (e.g., down shut feed) because of its low combustibility as a result of its low (10 m 2 /g) specific surface area. If the petroleum coke is directly combusted with 50% excess air, the flue gas mole percent composition would be approximately 12.8% CO 2 ; 7.0% O 2 ; 79.5% N 2 ; 0.2% NO x ; and 0.4% SO 2 . Excess O 2 and SO 2 species present in the flue gas can be effective to react with bitumen asphaltenes to produce sufficient sulfoxidation reactions to produce surfactant species effective to enhance bitumen recovery efficiency in accordance with the present invention. If necessary or desired, the SO 2 composition of the flue gas can be improved by oxidizing H 2 S or S to SO 2 ; both H 2 S and S are readily available in the northern Alberta oil sands region.
- petroleum coke may be gasified, and a fraction of the gasification product gas (the composition of which will depend on the selected gasification process) may be further processed to produce hydrogen (H 2 ) which may be used in known bitumen upgrading processes.
- the other fraction of the gasification product gas may be combusted to produce steam.
- the gaseous by-products would be mainly composed of CO 2 and N 2 .
- the N 2 content of the flue gas injected into subsurface oil sands seams, in accordance with the present invention, will have the effect of thermally insulating the seams.
- Nitrogen injected into a subsurface seam will tend to migrate to the interfacial region between the seam and overlying soil strata (overburden), forming a nitrogen "blanket” that helps to retain thermal heat (from injected steam) within the seam, thereby reducing thermal energy losses to the overburden and enhancing the efficiency of in situ thermal recovery processes.
- oxidation, sulfonation, and/or sulfoxidation reactions are initiated by exposing oil sands bitumen to oxidation agents such as air oxygen (O 2 ) air, ozone (Os), and/or sulfonation agents such as sulfur dioxide (SO 2 ) gas, sodium sulfite (Na 2 SOi) or sodium bi-sulfite (NaHSO 3 ), and/or petroleum coke utilization flue gas which is rich in excess air oxygen (O 2 ) and SO 2 .
- oxidation agents such as air oxygen (O 2 ) air, ozone (Os), and/or sulfonation agents such as sulfur dioxide (SO 2 ) gas, sodium sulfite (Na 2 SOi) or sodium bi-sulfite (NaHSO 3 ), and/or petroleum coke utilization flue gas which is rich in excess air oxygen (O 2 ) and SO 2 .
- bitumen asphaltenes containing these functional groups are known to have surfactant properties.
- bitumen asphaltenes to surfactant species in accordance with the present invention are not limited to oxidation, sulfonation, and/or sulfoxidation reactions.
- other surfactant species be formed by sulfomethylation of bitumen asphaltenes by introducing one or more sulfomethylation agents such as formaldehyde (H 2 CO) into ore-water slurries or subsurface oil sands seams, preferably in conjunction with the introduction of sulfonation and/or sulfoxidation agents.
- H 2 CO formaldehyde
- the sulfomethylation reactions result in the formation of hydrophilic methyl sulfonyl (C-CH 2 -SO 2 -O-) functional groups, which are effective to reduce surface and interfacial tensions.
- Other chemical agents having effective sulfomethylation properties may also be used, without departing from the scope of the present invention.
- the solubility of the oxidation, sulfonation and/or sulfoxidation and/or sulfomethylation reaction products may be increased by using pH- adjusting additives such as, but not limited to, sodium hydroxide (NaOH) or soda ash (Na 2 COs).
- pH-adjusting additives such as, but not limited to, sodium hydroxide (NaOH) or soda ash (Na 2 COs).
- NaOH sodium hydroxide
- Na 2 COs soda ash
- these water-soluble surfactant species promote the formation of bitumen-water emulsions under in situ recovery process conditions (e.g., ISC, SAGD, and CSS), thus improving bitumen recovery efficiency and also reducing the required water-to-oil (W/O) ratio.
- in situ recovery process conditions e.g., ISC, SAGD, and CSS
- the methods of the present invention can be used at a wide range of temperatures and pH values, by using /?H-adjusting chemicals such as sodium hydroxide (NaOH), sodium carbonate (Na 2 COs), and/or calcium hydroxide (Ca(OH) 2 ).
- the method of the invention uses air oxygen or an air- ozone mixture as an oxidation agent.
- the oxidation agent is preferably injected into ore slurry transportation pipelines.
- mined oil sands ore may be treated with ozone-air or other oxidation agents before being slurried with process water.
- the effectiveness of surfactant production in accordance with the invention by oxidation of bitumen asphaltenes may be further enhances by using preheating the air, ozone-air, or other oxidation before injection into oil sands ore- water slurries or subsurface oil sand seams.
- bitumen-water emulsions reduces surface and interfacial tension, which promotes the formation bitumen-water emulsions.
- the same reactions therefore can be used for the treatment of bitumen-water mixtures, as done in the oil sands ore-water slurry, to produce bitumen-water emulsions for the pipeline transportation of bitumen in the form of bitumen- water emulsions.
Abstract
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA2629039A CA2629039C (en) | 2004-12-09 | 2005-12-09 | Method for improving bitumen recovery from oil sands by production of surfactants from bitumen asphaltenes |
US11/720,782 US8043494B2 (en) | 2004-12-09 | 2005-12-09 | Method for improving bitumen recovery from oil sands by production of surfactants from bitumen asphaltenes |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA2,488,749 | 2004-12-09 | ||
CA2488749 | 2004-12-09 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2006060917A1 true WO2006060917A1 (en) | 2006-06-15 |
Family
ID=36577641
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/CA2005/001875 WO2006060917A1 (en) | 2004-12-09 | 2005-12-09 | Method for improving bitumen recovery from oil sands by production of surfactants from bitumen asphaltenes |
Country Status (3)
Country | Link |
---|---|
US (1) | US8043494B2 (en) |
CA (1) | CA2629039C (en) |
WO (1) | WO2006060917A1 (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7779914B2 (en) | 2008-12-10 | 2010-08-24 | Conocophillips Company | Process for producing heavy oil |
US7931800B2 (en) | 2007-03-14 | 2011-04-26 | Apex Engineering Inc. | Method for extraction of bitumen from oil sands using lime |
US8343337B2 (en) | 2008-10-29 | 2013-01-01 | E.I. Du Pont De Nemours And Company | Bitumen extraction process |
RU2483925C2 (en) * | 2007-10-31 | 2013-06-10 | Е.И.Дюпон Де Немур Энд Компани | Ionomer tubes of higher wear resistance |
Families Citing this family (10)
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US8003844B2 (en) * | 2008-02-08 | 2011-08-23 | Red Leaf Resources, Inc. | Methods of transporting heavy hydrocarbons |
US20120255887A1 (en) * | 2011-04-08 | 2012-10-11 | Frac Tech Services Llc | Method for Recovering Hydrocarbon from Tar Sand Using Nanofluid |
EP2850155B1 (en) | 2012-05-16 | 2018-04-04 | Chevron U.S.A., Inc. | Process for removing mercury from fluids |
AR094523A1 (en) | 2012-05-16 | 2015-08-12 | Chevron Usa Inc | PROCESS, METHOD AND SYSTEM TO SEPARATE FLUID MERCURY |
AU2013262694A1 (en) | 2012-05-16 | 2014-11-06 | Chevron U.S.A. Inc. | Process, method, and system for removing heavy metals from fluids |
US9447674B2 (en) | 2012-05-16 | 2016-09-20 | Chevron U.S.A. Inc. | In-situ method and system for removing heavy metals from produced fluids |
CA2823459C (en) | 2013-08-09 | 2015-06-23 | Imperial Oil Resources Limited | Method of using a silicate-containing stream from a hydrocarbon operation or from a geothermal source to treat fluid tailings by chemically-induced micro-agglomeration |
US9845669B2 (en) | 2014-04-04 | 2017-12-19 | Cenovus Energy Inc. | Hydrocarbon recovery with multi-function agent |
US10745623B2 (en) | 2016-01-29 | 2020-08-18 | Ecolab Usa Inc. | Methods for enhancing hydrocarbon recovery from oil sands |
US10815433B1 (en) * | 2019-10-15 | 2020-10-27 | King Abdulaziz University | Protic asphaltene ionic liquids as asphaltene stabilizer |
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CA2457603A1 (en) * | 2003-05-21 | 2004-11-21 | Continuum Environmental, Llc | Method and apparatus for separating bitumen from particulate substrates |
Family Cites Families (7)
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-
2005
- 2005-12-09 CA CA2629039A patent/CA2629039C/en not_active Expired - Fee Related
- 2005-12-09 WO PCT/CA2005/001875 patent/WO2006060917A1/en active Application Filing
- 2005-12-09 US US11/720,782 patent/US8043494B2/en not_active Expired - Fee Related
Patent Citations (7)
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US4494992A (en) * | 1983-06-20 | 1985-01-22 | Westvaco Corporation | Amphoterics as emulsifiers for bituminous emulsions |
CA2095037C (en) * | 1990-10-30 | 2002-03-19 | Jose L. Vega | Improving the color of surfactant agglomerates by admixing a solid bleaching agent |
US5622920A (en) * | 1991-12-02 | 1997-04-22 | Intevep, S.A. | Emulsion of viscous hydrocarbon in aqueous buffer solution and method for preparing same |
CA2306523A1 (en) * | 1999-10-22 | 2001-04-22 | Lirio Quintero | Low shear treatment for the removal of free hydrocarbons, including bitumen, from cuttings |
CA2421474A1 (en) * | 2002-03-11 | 2003-09-11 | The Governors Of The University Of Alberta | Method for recovering hydrocarbons from samples |
CA2433522A1 (en) * | 2002-06-25 | 2003-12-25 | Pat Page | Surfactant for bitumen separation |
CA2457603A1 (en) * | 2003-05-21 | 2004-11-21 | Continuum Environmental, Llc | Method and apparatus for separating bitumen from particulate substrates |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7931800B2 (en) | 2007-03-14 | 2011-04-26 | Apex Engineering Inc. | Method for extraction of bitumen from oil sands using lime |
RU2483925C2 (en) * | 2007-10-31 | 2013-06-10 | Е.И.Дюпон Де Немур Энд Компани | Ionomer tubes of higher wear resistance |
US8343337B2 (en) | 2008-10-29 | 2013-01-01 | E.I. Du Pont De Nemours And Company | Bitumen extraction process |
US7779914B2 (en) | 2008-12-10 | 2010-08-24 | Conocophillips Company | Process for producing heavy oil |
Also Published As
Publication number | Publication date |
---|---|
US20100147742A1 (en) | 2010-06-17 |
CA2629039C (en) | 2012-09-04 |
US8043494B2 (en) | 2011-10-25 |
CA2629039A1 (en) | 2006-06-15 |
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